Oligomeric urethane acrylates, their preparation and use

Abstract

An oligomeric urethane acrylate composition is disclosed. The composition comprises, on average per molecule, at least two structural units of the general formula I: R{—X—CH 2 —CH(—CH 2 —O—(O)—CR 1 ═CH 2 )[—O—C(O)—NH—]} n (I), where n is a number from 1 to 6, R is a monovalent to hexavalent organic radical, X is oxygen atom or —C(O)—O— radical linked by the carbon atom to the radical R, and R 1 is hydrogen atom, halogen atom, nitrile group, substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 6 carbon atoms, or substituted or unsubstituted aryl group having 6 to 10 carbon atoms. Also disclosed are processes for preparing and using the compositions.

1 . Urethane acrylate composition comprising, on average per molecule, at least two structural units of the general formula I:
   R{-X—CH 2 —CH(—CH 2 —O—(O)—CR 1 ═CH 2 )[—O—C(O)—NH-]} n   (I),   
     wherein
 n is a number from 1 to 6; 
 R is an organic radical selected from the group consisting of monovalent to hexavalent, low molecular mass and oligomeric organic radicals; 
 X is selected from the group consisting of oxygen atom and —C(O)—O—radical linked by the carbon atom to the radical R; and 
 R 1  is selected from the group consisting of hydrogen atom, halogen atom, nitrile group, substituted and unsubstituted alkyl group having 1 to 6 carbon atoms, substituted and unsubstituted cycloalkyl group having 3 to 6 carbon atoms, and substituted and unsubstituted aryl group having 6 to 10 carbon atoms. 
 
   
   
       2 . The urethane acrylate composition of  claim 1 , further comprising at least one structural units of the general formula (II) linked to the organic radical R:
   —X—CH 2 —CH(—OH)(—CH 2 —O—(O)—CR 1 ═CH 2 )  (II).   
   
   
       3 . The urethane acrylate composition of  claim 1 , prepared by reacting:
 at least one compound of the general formula III:
   R[—X—CH 2 —CH(—OH)(—CH 2 —(O)—CR 1 ═CH 2 )] n   (III), 
   in which the index n and the variables R, X, and R 1  are as defined above; and at least one polyisocyanate having at least two isocyanate groups, in a compound III:polyisocyanate ratio corresponding to an OH:NCO equivalent ratio >1 to 5.   
   
   
       4 . The urethane acrylate of  claim 3 , wherein n is an integer from 1 to 5. 
   
   
       5 . (canceled) 
   
   
       6 . The urethane acrylate composition of  claim 1 , wherein the organic radical R is selected from the group consisting of substituted and unsubstituted radicals, radicals free from heteroatoms and radicals having at least one heteroatom Y, radicals free from and radicals having at least one divalent, linking radical R 2  and radicals consisting of and radicals including at least one radical R 3  selected from the group consisting of alkyl, cycloalkyl, and aryl radicals. 
   
   
       7 . The urethane acrylates of  claim 6 , wherein the heteroatom Y is selected from the group consisting of boron, silicon, nitrogen, phosphorus, oxygen, and sulfur. 
   
   
       8 . The urethane acrylate composition of  claim 6 , wherein the divalent linking radical R 2  is selected from the group consisting of carboxylic ester, thiocarboxylic ester, carbonate, thiocarbonate, phosphate, thiophosphate, phosphonate, thiophosphonate, phosphite, thiophosphite, sulfonate, amide, amine, thioamide, phosphoramide, thiophosphoramide, phosphonamide, thiophosphonamide, sulfonamide, imide, urethane, hydrazide, urea, thiourea, carbonyl, thiocarbonyl, sulfone, sulfoxide, and siloxane groups. 
   
   
       9 . The urethane acrylates of  claim 1 , wherein the variable R 1  is selected from the group consisting of a hydrogen atom and a methyl group. 
   
   
       10 . The urethane acrylate composition of  claim 3 , wherein the at least one compounds of the general formula III is prepared by reacting:
 at least one compounds of the general formula IV: and   
     
       
         
         
             
             
         
       
       at least one compound of the general formula V:
   H—O—(O)—CR 1 ═CH 2   (V). 
 
     
   
   
       11 . The urethane acrylate composition of  claim 3 , wherein the polyisocyanate further comprises radicals selected from the group consisting of blocked isocyanate groups and radicals R 4  containing bonds which can be activated with actinic radiation. 
   
   
       12 . The urethane acrylate composition as claimed in  claim 11 , wherein radicals R 4  have the general formula VI:
   —O—(O)—CR 1 ═CH 2   (VI).   
   
   
       13 . The urethane acrylate as claimed in of  claim 1 , which are free-radically polymerizable. 
   
   
       14 . The urethane acrylate composition as claimed in  claim 11 , wherein the actinic radiation is at least one selected from the group consisting of UV radiation and electron beams. 
   
   
       15 . A process for preparing urethane acrylates composition as claimed in  claim 1 , comprising reacting at least one compound of the general formula III:
   R[—X—CH 2 —CH(—OH)(—CH 2 —O—(O)—CR 1 ═CH 2 )] n   (III),   with at least one polyisocyanate having at least two isocyanate groups, in a compound III:polyisocyanate ratio corresponding to an OH:NCO equivalent ratio >1 to 5.   
   
   
       16 . The process as claimed in  claim 15 , wherein the OH:NCO equivalent ratio is 1.5 to 4. 
   
   
       17 . The process as claimed in  claim 15 , wherein the at least one compounds of the general formula III are prepared by reacting at least one compounds of the general formula IV: 
     
       
         
         
             
             
         
       
       with at least one compounds of the general formula V:
   H—O—(O)—CR 1 ═CH 2   (V). 
 
     
   
   
       18 . The process of using of the urethane acrylate composition as claimed in  claim 1  as a material which is free-radically curable thermally, with actinic radiation or a combination of thermally and with actinic radiation. 
   
   
       19 . The process as claimed in  claim 18 , wherein the material which is free-radically curable thermally, with actinic radiation or a combination of thermally and with actinic radiation is substantially free from organic solvents and reactive diluents which can be activated with actinic radiation. 
   
   
       20 . The process as claimed in  claim 19 , wherein the curable materials is cured under an oxygen-depleted atmosphere. 
   
   
       21 . (canceled) 
   
   
       22 . (canceled) 
   
   
       23 . (canceled) 
   
   
       24 . The process as claimed in  claim 19 , wherein the curable materials serves to produce thermoset materials. 
   
   
       25 . The process as claimed in  claim 24 , wherein the thermoset materials are coatings, adhesive layers, seals, sheets or moldings. 
   
   
       26 . The process as claimed in  claim 25 , wherein the coatings are selected from the group consisting of glossily clear transparent and flat transparent primer coatings, glossy opaque and flat opaque basecoats, glossily clear transparent and flat transparent topcoats, and glossy opaque and flat opaque topcoats. 
   
   
       27 . (canceled)